JPH01318017A - Liquid aminated hydrogenated diene polymer, preparation thereof and composition containing the same - Google Patents

Abstract

PURPOSE:To enhance curing speed and to make it possible to form a cured product having excellent heat resistance, weatherability, water resistance, rubber elasticity, etc., by reacting a liq. aminated hydrogenated diene polymer having a specified molecular structure with an org. polyisocyanate compd. CONSTITUTION:This liq. aminated hydrogenated diene polymer has the following structure. Namely, it is a polymer wherein 80% or more of the carbon-carbon double bonds of the main chain of the liq. polymer having a bound vinyl group content of 20% or lower is hydrogenated and its number-average MW and the average number of amino groups per molecule are 500-10,000 and 1.5 or larger, respectively. This polymer is pref. formed by means of the following method. Namely, liq. cyano group-contg. diene polymer wherein a bound vinyl group content is 20% or lower, the number-average MW after hydrogenation is 500-10,000 and an average number of cyano groups per molecule is 1.50 or larger is hydrogenated to convert the cyano groups to amino groups and a the same time to hydrogenate 80% or more of the carbon-carbon double bonds of the main chain.

Description

[Detailed description of the invention] [Industrial application field] The present invention has excellent operability and high reactivity, and the cured product of these and an organic polyisocyanate compound has excellent mechanical properties, heat resistance, weather resistance, and water resistance. The present invention relates to an excellent hydrogenated liquid diene polymer containing amino groups, a method for producing the same, and a composition containing the same.

[Prior art] Liquid diene polymers have fluidity at room temperature, and after forming a three-dimensional network structure with sulfur, peroxide, etc.
It exhibits the same physical properties as ordinary solid rubber. Liquid diene polymers with functional groups in their molecules are also commercially available, and can be used as various polymer modifiers using these functional groups, or as cured products that form three-dimensional network structures using chemical reactions of the functional groups. It is widely used as a raw material for reactive liquid diene polymers.

Functional groups introduced include hydroxyl groups (011 groups), carboxyl groups (COO! groups), and liquid diene polymers having hydroxyl groups are particularly useful as polyol components of polyurethane.

However, since these liquid diene-based polymers have carbon-carbon double bonds in their molecular chains, there have been problems with the heat resistance, weather resistance, etc. of cured products using these as one of the raw materials. Hydrogenated diene polymers containing hydroxyl groups, such as hydrogenated polybutadiene containing hydroxyl groups, are known in which carbon-carbon double bonds are hydrogenated in order to improve this drawback.

Polyurethane using this hydroxyl group-containing hydrogenated diene polymer as a polyol has superior heat resistance, water resistance, weather resistance, electrical properties, etc. compared to ordinary polyurethane, but the hydroxyl group in the liquid diene polymer It cannot be said that the curing speed due to the reaction between the organic polyisocyanate compound and the organic polyisocyanate compound is sufficiently high. Therefore, the use of hydroxyl group-containing hydrogenated diene polymers in reaction injection molding (RIM), reinforced reaction injection molding (R-RIM), etc., which have been significantly developed in recent years, has been limited.

[Problems to be Solved by the Invention] The present invention addresses the problems associated with hydroxyl group-containing hydrogenated diene polymers, namely that polyurethanes obtained using them have poor heat resistance and weather resistance. To provide an excellent hydrogenated liquid diene polymer which solves problems such as insufficient curing speed due to reaction with an isocyanate compound, an efficient method for producing the same, and a composition containing the same. With the goal.

[Means for Solving the Problems] According to the present invention, the above objects are achieved by an amino group-containing hydrogenated liquid diene polymer.

That is, the present invention according to claim 1 has a vinyl bond amount of 20%.
A polymer in which 80% or more of the carbon-carbon double bonds in the main chain of the following amino group-containing liquid diene polymers are hydrogenated, with a number average molecular weight of 500 to 10,000 and an average number of amino groups per molecule. is 1.50 or more.

The present invention according to claim 2 is a cyano group-containing liquid diene system having a vinyl bond content of 20% or less, a number average molecular weight after hydrogenation of 500 to 10,000, and an average number of cyano groups per molecule of 1.50 or more. An amino group with a vinyl bond content of 20% or less, which is characterized by hydrogenating a polymer to convert a cyano group into an amino group and at the same time hydrogenating 80% or more of the carbon-carbon double bonds in the main chain. 8 of the carbon-carbon double bonds in the main chain of the hydrogenated liquid diene polymer containing
Production of a polymer that is 0% or more hydrogenated, has a number average molecular weight of 500 to 10,000, and has an average number of amino groups per molecule of 1.50 or more (i.e., the polymer according to claim 1). The present invention provides a method.

The present invention according to claim 3 is a polymer in which 80% or more of the carbon-carbon double bonds in the main chain of an amino group-containing liquid diene polymer having a vinyl bond content of 20% or less are hydrogenated,
Provides a composition containing a polymer having a number average molecular weight of 500 to 10,000 and an average number of amino groups per molecule of 1.50 or more (i.e., the polymer according to claim 1), and an organic polyisocyanate compound. It is.

The present invention will be explained in more detail below.

The amino group-containing hydrogenated liquid diene polymer of the present invention needs to have a vinyl bond content of 20% or less.

If the amount of vinyl bonds exceeds 20%, mechanical properties such as rubber elasticity at low temperatures of the cured product with the organic polyisocyanate compound will deteriorate. Preferably, the amount of vinyl bonds is 10% or less. The microstructure of 1.4-cis, 1.4-) lance, 1,2-vinyl and 3,4-vinyl is 'II-NM.
This is determined from the R spectrum.

The hydrogenation rate of the hydrogenated liquid diene polymer containing amino groups is 80
% or more. Less than 80% carbon-
Heat resistance due to heat or light due to carbon double bonds,
Deterioration of weather resistance becomes a problem. Preferably the hydrogenation rate is 90%
That's all.

The amino group-containing hydrogenated liquid diene polymer of the present invention needs to have a number average molecular weight of 500 to 10,000. When the number average molecular weight is less than 500, the cured product with the organic polyisocyanate compound does not have good rubber elasticity. If it exceeds 10,000, the hydrogenated liquid diene polymer will not exhibit good fluidity.

The number average molecular weight of the hydrogenated liquid diene polymer is preferably 1,000 to 5,000.

Number of amino groups in hydrogenated liquid diene polymer containing amino groups (
・The average number of amino groups per molecule) must be 1.50 or more. When the number of amino groups is less than 1.50, sufficient crosslinking cannot be obtained in the reaction with the organic polyisocyanate compound, resulting in problems such as poor mechanical strength of the cured product. Since it is difficult in practice to increase the number of amino groups much, it is considered that the expression 1.50 or more is sufficient. However, taking into consideration empirical considerations, if the number of amino groups is too large, the crosslinking density becomes too high and the cured product does not exhibit good rubber elasticity. Therefore, preferably the number of amino groups is 1.80 to 5.0.

This amino group may be located either at the end of the molecular chain or within the chain, but those located at the ends, particularly at both ends, are preferably used.

Here, the hydrogenated liquid diene polymer having an amino group is a hydrogenated liquid diene polymer having an amino group in the molecular chain of the polymer, especially at the terminal, and especially if it is a hydrogenated liquid diene polymer having an amino group in the molecular chain of the polymer, monomers There are no restrictions on the presence or absence of functional groups. Liquid diene polymers before hydrogenation include diene polymer polymers, copolymers of these diene monomers,
Further examples include copolymers of these diene monomers and non-conjugated double bond-containing monomers. Furthermore, it also includes those modified by introducing an unsaturated carboxylic acid such as maleic anhydride or a derivative thereof through a reaction with a carbon-carbon double bond of these diene polymers, such as an ene reaction. It is. In the above copolymer of diene monomers, the mutual ratio of the monomers may be arbitrary; in the case of a copolymer with a monomer containing a non-conjugated double bond, the amount of the monomer containing a non-conjugated double bond to be used is relative to the diene monomer. It is generally 50% or less by weight. If it exceeds 50%, the rubber elasticity of the cured product obtained by the reaction between the copolymer and the organic polyisocyanate compound will be impaired, which is not preferable. Further, when an unsaturated carboxylic acid or a derivative thereof is used, the amount used is preferably 15% or less by weight relative to the diene monomer.

Specifically, diene monomers include butadiene, isoprene, cyclohexa-1,3-diene, chloroprene, silyl group-containing butadiene, azabutadiene, etc.; non-conjugated double bond-containing monomers include ethylene, propylene, butene, etc. , isobutylene, styrene, methylstyrene, p-chloromethylstyrene, acrylonitrile, methyl acrylate, hydroxyethyl acrylate, glycidyl methacrylate, and the like.

In addition, specific examples of liquid diene polymers before hydrogenation include butadiene homopolymer, isoprene homopolymer,
butadiene-isoprene copolymer, butadiene-styrene copolymer, butadiene-isoprene copolymer,
styrene-butadiene-styrene block copolymer,
styrene-isoprene-styrene block copolymer,
Examples include butadiene-acrylonitrile copolymer, isoprene-acrylonitrile copolymer, isoprene-methyl acrylate copolymer, isoprene-hydroxyethyl methacrylate copolymer, and the like.

The novel amino group-containing hydrogenated liquid diene polymer according to claim 1 can be prepared by several methods, such as claim 2 as described below.
It can be produced by the method described.

That is, hydrogenating a cyano group-containing liquid diene polymer having a vinyl bond content of 20% or less, a number average molecular weight after hydrogenation of 500 to 10,000, and an average number of cyano groups per molecule of 1.50 or more. It can be manufactured by

First, the cyan group-containing liquid diene polymer, which is a raw material, can be obtained by various methods. For example, azobisisobutyronitrile (AIBN), 1,1'-
Azobiscyclohexane-1-carbonitrile, 2.2
'-azobis(2,4-dimethylvaleronitrile), 2
．． Using a compound having a cyan group (CN group) on both sides of an azo group such as 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) as an initiator, a diene monomer,
Further, a cyano group-containing liquid diene polymer can be obtained by radical polymerization of a diene monomer and a monomer containing a nonconjugated double bond. The appropriate amount of the polymerization initiator to be used is 0.1 to 20 g per 100 g of the diene monomer or 100 g of the diene monomer and the non-conjugated double bond monomer. Although polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction.

As the solvent, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, water, alcohols such as ethanol and 2-propanol, or mixtures thereof are usually used.

Suitable reaction temperature is 60 to 100°C and reaction time is 1 to 10 hours. After the reaction is completed, the solvent is distilled off under heating to easily obtain a cyano group-containing liquid diene polymer.

Next, the amino group-containing hydrogenated liquid diene polymer is obtained by adding the cyano group-containing liquid diene polymer produced as described above to the cyano group in the molecular chain and carbon-carbon by a known method using a homogeneous catalyst or a heterogeneous catalyst. It can be obtained by simultaneously hydrogenating the double bond.

When using a homogeneous catalyst, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent, and the reaction temperature is from room temperature to 150'C under a hydrogen pressure of from normal pressure to 50 kg/cm2. A hydrogenation reaction takes place. As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal halide and an alkylated product of aluminum, an alkaline earth metal, or an alkali metal is used in an amount of 0.01 to 0.1 mol per double bond of the polymer.
Use about χ. The reaction is completed in 1 to 50 hours. After the reaction is complete, acidic water is added to the container and stirred vigorously to dissolve the catalyst used in the water. Of the two phase-separated phases, the aqueous phase is removed and the solvent is distilled off to obtain the desired amino group-containing hydrogenated liquid diene polymer.

When using a heterogeneous catalyst, water, saturated hydrocarbons such as hexane, cyclohexane, benzene, toluene,
Aromatic hydrocarbons such as xylene, diethyl ether, T
Using ethers such as HF and dioxane, alcohols such as ethanol and isopropanol, or mixtures thereof as a solvent, the reaction temperature is from normal temperature to 250°C and at normal pressure to 250°C.
The hydrogenation reaction is carried out under a hydrogen pressure of 0.00 kg/cm2. As a heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium, or ruthenium is used alone or supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon, and the amount used is 0 based on the weight of the polymer. .5～
10ivtχ is appropriate.

The reaction is usually completed in 1 to 50 hours. After the reaction is completed, the reaction product is extracted from the container and the catalyst is filtered off.
By distilling off the solvent overnight, the desired amino group-containing hydrogenated liquid diene polymer is obtained.

The present invention as set forth in claim 3 relates to a composition containing an amino group-containing hydrogenated liquid diene polymer that satisfies the predetermined conditions obtained as described above, and an organic polyisocyanate compound.

Examples of the organic polyisocyanate compound used here include organic polyisocyanate compounds having two or more isocyanate groups in one molecule, such as tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, phenylene diisocyanate, dicyclohexylmethane diisocyanate, etc. .

The composition of the present invention can be crosslinked, cured, and used for various purposes.

The production of this cured product proceeds by adding an organic polyisocyanate compound to the amino group-containing hydrogenated liquid diene polymer obtained by the present invention and reacting a part or all of it.

At this time, a method of mixing and curing an amino group-containing hydrogenated liquid diene polymer and an organic polyisocyanate (one-shot method) or a method of curing the amino group of the amino group-containing hydrogenated liquid diene polymer and the isocyanate group of the organic polyisocyanate compound A method of reacting in advance to form a polymer (prepolymer) having isocyanate groups and curing this using a curing agent (prepolymer method) is adopted.

In the case of the one-shot method, the amino group (Nl2) in the hydrogenated liquid diene polymer and the isocyanate group (NGO) in the organic polyisocyanate compound have a molar ratio of NGO/
It is used in a range of about NH2=0.5 to 5.0. If the ratio is less than 0.5, sufficient strength of the cured product cannot be obtained, and conversely, if the ratio exceeds 5, the crosslinking density becomes too high and a cured product with sufficient elasticity cannot be obtained.

Further, when curing, it is possible to use a chain extender in addition to the organic polyisocyanate compound, and there is no particular restriction on the amount used, but based on 100 parts by weight of the hydrogenated liquid diene polymer containing amino groups, It is preferably used in a range of 1 to 250 parts by weight.

In the case of the prepolymer method, the NCO/N11z molar ratio is in the range of 2.0 to 5.0. If the ratio is less than 2.0, unreacted amino groups remain, resulting in problems such as a significant increase in viscosity or hardening during the reaction, and progress in hardening during storage, which is undesirable. On the other hand, if it exceeds 5.0, the cured product will lose its rubber elasticity, which is not preferable.

This first reaction is carried out by stirring the mixture of the amino group-containing hydrogenated liquid diene polymer and the organic polyisocyanate compound at a temperature of usually room temperature to 100°C for 001 to 10 hours.

The hydrogenated liquid diene polymer (prepolymer) having isocyanate groups obtained above is crosslinked and cured using water and a chain extender (polyol compound or polyamino compound). When these are used as crosslinking agents, it is preferable to use them so that the nominal molar ratio OH/NGO or NIIZ/NGO of the hydroxyl group in the polyol compound or the amino group in the polyamino compound to the isocyanate group is in the range of 0.5 to 5.0. .

Here, in both the prepolymer method and the one-shot method, the chain extenders include 1,4-butanediol, bentanediol, hexanediol, ethylene glycol,
Polyol compounds including alkanediols such as propylene glycol, alkanediaminos such as tetramethylene diamino and hexamethylene diamino, and polyamino compounds such as aromatic diamino such as 4,4-diaminodiphenyl are used.

The conditions for curing are room temperature to 250°C in both the prepolymer method and the one-shot method.
Preferably 0.1-20 at a temperature of 60°C-150°C
done in time.

In addition, during curing, polyester polyols such as ethylene adipate and butylene adipate, polyether polyols such as polypropylene glycol and polyethylene glycol are used for the purpose of improving adhesion to glass and metals, and hydroxyl group-containing polyols are used for the purpose of improving the hardness of the sheet. Diene polyols such as polybutadiene and hydrogenated diene polyols such as hydroxyl group-containing hydrogenated polybutadiene are added in an amount of 50% by weight or less, preferably 30% by weight or less, based on the amino group-containing hydrogenated liquid diene polymer. It is also possible to do so.

In addition, crosslinking aids such as dibutyl/tin dilaurate, reinforcing agents such as carbon black, silica, and clay, fillers such as calcium carbonate, anti-aging agents such as BIT, plasticizers such as paraffin oil, tackiness, and adhesives. It is also possible to add tackifier resins such as rosin resins, terpene resins, and petroleum resins to improve properties. There is no limit to the amount of these to be used as long as it does not impair the purpose and effect of the present invention, and it is determined appropriately depending on the purpose, but usually the crosslinking agent is added to 100 parts by weight of the hydrogenated liquid diene polymer containing amino groups. 0 to 5 parts by weight of the agent, 0 to 500 parts by weight of the reinforcing agent, 0 to 500 parts by weight of the filler, 0 to 10 parts by weight of the antiaging agent, 0 to 300 parts by weight of the plasticizer, and 0 parts by weight of the tackifying resin. ~
It is appropriate to use 300 parts by weight.

The cured product produced in this way, which contains an amino group-containing hydrogenated liquid diene polymer and an organic polyisocyanate compound as essential components, has excellent heat resistance, weather resistance, water resistance, electrical properties, and good rubber elasticity. Furthermore, the applications in which cured products obtained from hydroxyl group-containing hydrogenated liquid diene polymers and organic polyisocyanate compounds are currently used include:
In the field of caulking materials, sealants, coating materials, electrical and electronic component sealants, etc. for civil engineering and construction, shipbuilding, etc.
It has the advantage of curing at a lower temperature, shortening the molding cycle, and saving energy. In addition, this amino group-containing hydrogenated liquid diene polymer has a sufficiently high curing rate due to an extremely fast reaction with organic polyisocyanate compounds, so it can be used for completely new applications, i.e., combining hydroxyl group-containing hydrogenated liquid diene polymers with organic polyisocyanate compounds. The use of RIM and R-RIM, whose use was limited due to insufficient curing speed in the reaction of Its industrial significance is extremely great, as molded products can be formed economically.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

The number average molecular weight of the cyano group-containing liquid diene polymer or amino group-containing hydrogenated liquid diene polymer used was measured using a vapor pressure osmometer (Vapour Pressure Osmometer).
The value measured at ome ter) was used. In addition, the amino group concentration was measured by titration with perchloric acid. Therefore, the average number of amino groups per molecule, that is, the number of amino groups, is given by the following formula.

Amino group=amino group concentration (meq/g)

The calculation formula is shown below.

Hydrogenation ratio - (AB) ÷ AX100 Here, A: Iodine value of liquid diene polymer containing diamino group B: Iodine value of hydrogenated liquid diene polymer containing diamino group.

In addition, in the following Examples, Application Examples, and Comparative Examples, "reaction equivalent ratio" refers to the ratio of the isocyanate group equivalent in the organic polyisocyanate compound to the amino group equivalent in the amino group-containing hydrogenated liquid diene polymer, that is, the NCO /NH2
or the ratio of the isocyanate group equivalent in the organic polyisocyanate compound to the hydroxyl group equivalent in the hydroxyl group-containing hydrogenated liquid diene polymer, that is, the value of NGOloH.

Example 1 100 g of cyano group-containing liquid polyisoprene with a vinyl bond content of 7.4χ obtained by radical polymerizing isoprene monomer at 90'C for 15 hours using azobisisobutyronitrile as an initiator and toluene as a solvent. was hydrogenated using 10 g of Raney cobalt catalyst and dioxane as a solvent at 150'C for 115 hours at a hydrogen pressure of 50 KB/cm2 to obtain a number average molecular weight of 3,000, amino acid, 11 degrees of 0.73 meq/g, and number of amino groups of 2.19.
, an amino group-containing hydrogenated liquid polyisoprene having a hydrogenation rate of 98χ was obtained.

As a result of infrared absorption spectrum analysis (IR analysis), cyano group-containing liquid polyisoprene showed absorption of cyano groups at 2250 cm-', but its hydrogenated product showed absorption of cyano groups at 2250 cm-'. disappears,
Instead, the amino group N-
Absorption of H stretching vibration appeared. Together with the hydrogenation rate determined from the iodine value, it was confirmed that the obtained polymer was hydrogenated liquid polyisoprene having amino groups.

Application Example 1 Number average molecular weight 3,000, amino group concentration 0.73 meq/g, number of amino groups 2.19, obtained in Example I.
Amino group-containing hydrogenated liquid polyisoprene 1 with a hydrogenation rate of 98χ
00g, and Coronate T-80 (TDI manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate concentration 11.5 meq/
g) 7.0g (reaction equivalent ratio = 1.10) was mixed and degassed at room temperature, quickly poured into a press that had been heated to 100°C, and reacted for 20 minutes to form a cross-linked product with a thickness of 2. I got it. The results of measuring the physical properties of the obtained crosslinked product are shown in Table 1, and the results of heat resistance and weather resistance tests are shown in Table 2.

From the above, it can be seen that the amino group-containing hydrogenated liquid polyisoprene exhibits good reactivity with organic polyisocyanate compounds. In addition, the cured product obtained in Application Example 1 was
It can be seen from the table that it has good rubber elasticity, and from Table 2 it can be seen that it has good heat resistance and weather resistance.

Table 1 Crosslinking conditions 100°Cl2O Addition of crosslinking aid None Tensile strength Kg/cπ223 Tear strength Kg/cm 11100χ Tensile stress Kg/cm" 12 Elongation χ 2
00 Hardness JIS A 49 Measurement conditions: Instron tensile testing machine Initial length 2 cm
+Tensile speed 10mn+/win.

The following is Table 2 of the meeting, according to Weathermae (Associate: Engineering) Comparative Example 1 Vinyl obtained by radical polymerizing isoprene monomer at 130°C for 16 hours using hydrogen peroxide as an initiator and isopropyl alcohol as a solvent. Hydroxyl group-containing liquid polyisoprene with a bonding amount of 8.9χ was heated to 150% by using heptane as a solvent using palladium-carbon (Japan Engelhardt Co., Ltd. product, palladium content 5χ).
' By hydrogenating at a C1 hydrogen pressure of 10 kg/cm2 for 15 hours, the number average molecular weight was 3,100 and the hydroxyl group concentration was 0.
A hydrogenated product of liquid polyisoprene containing hydroxyl groups was obtained with a yield of 75 me/g, a number of hydroxyl groups of 2.33, and a hydrogenation rate of 97χ.

100 g of this hydrogenated product and 2 g of Coronate T-807 (reaction equivalent ratio -1.10) were mixed and defoamed at room temperature in the same manner as in Application Example 1, and then reacted on a press for 20 minutes.
No crosslinked product was obtained due to insufficient crosslinking.

Therefore, 100g of this hydrogenated product and Coronate T-807,
2g and 0.1g of dibutyltin dilaurate as a crosslinking aid.
After mixing and defoaming at room temperature, the mixture was reacted on a press at 120° C. for 160 minutes to obtain a crosslinked product with a thickness of 2 mm. Table 3 shows the results of measuring the physical properties of the obtained crosslinked product.

As is clear from the comparison with Application Example 1, the hydroxyl group-containing hydrogenated liquid polyisoprene of Comparative Example 1 is inferior to the amino group-containing hydrogenated liquid polyisoprene of Application Example 1 in its reactivity with organic polyisocyanate compounds. , and this comparative example 1
The crosslinked product obtained in Example 1 is inferior in physical properties to the crosslinked product obtained in Application Example 1.

■Table 1 Crosslinking conditions 120°C 160 minutes Addition of crosslinking aid Tensile strength with addition of dibutyltin dilaurate
Kg/cm210 Tear strength Kg/cm 5100χ Tensile stress Kg/cm" 3 Elongation χ 30
0 Hardness JIS A 21 Measurement conditions: Instron tensile testing machine, initial length 2 cm, tensile speed 10 mm/min.

Comparative Example 2 Hydroxyl group-containing liquid polyisoprene with a vinyl bond content of 8.6χ obtained by radical polymerizing isoprene monomer at 130°C for 16 hours using hydrogen peroxide as an initiator and isopropyl alcohol as a solvent was dissolved in toluene. Then, by adding catalytic amounts of BF, Et20, and Kanoquinone, and reacting aniline at 150'C for 28 hours, a number average molecular weight of 3,100 and an amino group concentration of 0.68 were obtained.
An amino group-containing liquid polyisoprene having a meq/g and an amino group number of 2.10 was obtained.

100 g of this amino group-containing liquid polyisoprene and 5 g of Coronate T-806 (reaction equivalent ratio -1.10) were mixed at room temperature, defoamed, and quickly poured into a press that had been heated to 100°C. The reaction was carried out for 20 minutes to obtain a crosslinked product with a thickness of 2 mm. The results of measuring the physical properties of the obtained crosslinked product are shown in Table 4, and the results of heat resistance and weather resistance tests are shown in Table 5.

As is clear from Tables 1 and 4, the crosslinked product obtained in Comparative Example 2 had a
The physical properties of the crosslinked product are poor. Furthermore, as is clear from Tables 2 and 5, the crosslinked product obtained in Comparative Example 2 is different from Application Example 1.
It is also inferior in heat resistance and weather resistance compared to the crosslinked product obtained in .

Star soil surface crosslinking conditions 100°Cl2O No addition of crosslinking aid Tensile strength Kg/cm218 Tear strength Kg/cm 10100χ Tensile stress Kg/cm27 Elongation χ 300 Hardness JIS 824 Measurement conditions: Instron tensile tester initial Length 2cm, tensile speed 10mm/min.

Table 5 11 (by Weathermae) [Effects of the invention] The amino group-containing hydrogenated liquid diene polymer according to claim 1 has excellent operability and is rich in reactivity, and its organic polyisocyanate compound The cured product has excellent mechanical properties, heat resistance, weather resistance, water resistance, etc. Wood polymers have a sufficiently high curing speed with organic polyisocyanate compounds, so they can be used for reaction injection molding and reinforced reaction injection molding.

The invention according to claim 2 is characterized by an efficient method for producing the amino group-containing hydrogenated liquid diene polymer, which comprises the amino group-containing hydrogenated liquid diene polymer according to claim 3, and an organic polyisocyanate compound. The composition improves mechanical properties, heat resistance, weather resistance, water resistance, electrical properties,
Provides a cured product with excellent rubber elasticity. This cured product can be similarly used in applications where cured polyurethane (polyurethane) obtained from a hydroxyl group-containing hydrogenated liquid diene polymer and an organic polyisocyanate compound is currently used. This composition has the advantage that curing proceeds at a lower temperature than in the case of producing polyurethane, which leads to shortening of molding cycles and energy saving. It can also be used in reaction injection molding and reinforcing reaction injection molding, whose use has been limited due to insufficient curing speed in the production of polyurethane.

Patent applicant: Kuraray Co., Ltd. Agent: Patent Attorney Ken Motoda

Claims (1)

[Scope of Claims] 1. A polymer in which 80% or more of the carbon-carbon double bonds in the main chain of an amino group-containing liquid diene polymer having a vinyl bond content of 20% or less is hydrogenated, and has a number average molecular weight is 50
0 to 10,000, with an average number of amino groups per molecule of 1
．． 50 or higher. 2. Hydrogenating a cyano group-containing liquid diene polymer that has a vinyl bond content of 20% or less, a number average molecular weight after hydrogenation of 500 to 10,000, and an average number of cyano groups per molecule of 1.50 or more. 2. The method for producing a polymer according to claim 1, wherein 80% or more of the carbon-carbon double bonds in the main chain are hydrogenated at the same time as cyano groups are converted to amino groups. 3. A polymer in which 80% or more of the carbon-carbon double bonds in the main chain of an amino group-containing liquid diene polymer having a vinyl bond content of 20% or less and a number average molecular weight of 50
0 to 10,000, with an average number of amino groups per molecule of 1
．． 50 or more, and an organic polyisocyanate compound.